Hydropentalenyl manganese tricarbonyl compounds and processes for same



s 100 213 HYDRorENTALaNrL MANGANESE TRKCAR- BONYL COMPOUNDS rnocnssns Fen SAME Thomas H. Coifield, Heidelberg, Germany, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia N Drawing. Filed Jan. 12, 1960, Ser. No. 1,853 Claims. (Cl. 260-429) The compound is formed by reacting acetylene with a manganese carbonyl compound having the formula ZMn(CO) Z is a monovalent substituent group such as an alkyl, aryl, alkaryl, aralkyl, acyl, cycloalkyl, alkenyl, alkynyl or halogen group. These groups may contain various substituents which may be hydrocarbons or nonhydrocarbon groups. The monovalent substituent .group, Z, preferably contains up to about 16 carbon atoms. Certain substituent groups, however, such as the halogen groups, contain no carbon atoms. The substituent groups can contain double and triple bonds and, therefore, can be alkenyl or alkynyl radicals.

Typical of the compounds represented by ZMn(CO) which are reactants in my process, are methylmanganese pentacarbonyl, chloromanganese pentacarbonyl, bromomanganese pentacorbonyl, benzoylmanganese pentacarbonyl, phenylmanganese pentacarbonyl, ethylmanganese pentacarbonyl, propionylmanganese pentacarbonyl, benzylmanganese pentacarbonyl, perfluoromcthylmanganese pentacarbonyl, acrylylmanganese pentacarbonyl, iodomanganese pentacarbonyl and the like.

Although not bound by any theory as to the precise nature of the reaction involved in my process, it is believed to be best represented by Way of the following equation.

As depicted above, the reaction involves four moles of acetylene which react with one mole of a manganese carbonyl compound, ZMn(CO) to yield one mole of dihydropentalenyl manganese tricarbonyl.

Since the manganese carbonyl is the more expensive of the two reactants utilized in my process, it is desirable to use excess quantities of the acetylene to increase the yield of product based on the amount of the manganese carbonyl compound employed. Generally, from eight to 50 moles of acetylene are employed for each mole of the manganese carbonyl reactant. The quantities of reactants ice employed are not critical, however, and greater or lesser amounts of the acetylene may be used if desired.

In general, my process is carried out in the presence of a non-reactive solvent. The nature of the solvent is not critical, although it has been found that the polar solvents such as acetone, tetrahydrofuran and the dimethyl ether of diethylene glycol are preferred since the manganese carbonyl reactant is quite soluble in such solvents.

Typical of reaction solvents which may be employed in my process are high boiling saturated hydrocarbons such as n-octane, n-decane, and other parafiinic hydrocarbons having up to about 20 carbon atoms such as eicosane, pentadecane, and the like. Typical aromatic solvents are mesitlyene, benzene, toluene, xylenes, either pure or mixed and the like. Typical ether solvents are ethyl octyl ether, ethyl hexyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, trioxane, tetrahydrofuran, ethylene glycol dibutyl ether and the like. Ester solvents which may be employed include pentyl butanoate, ethyl decanoate, ethyl hexanoate, and the like. Silicone oils such as the dimethyl polysiloxanes, bis(chlorophenyl) polysiloxanes, hexapropyl disilane, and diethyldipropyldiphenyldisilane may also be employed. Other ester solvents are those derived from succinic, maleic, glutaric, adipic, pimelic, suberic, azelaic, sebacic and pinic acids. Specific examples of such esters are di(2-ethylhexyl) adipate, di-(2-ethylhexyl) azelate, di-(2 ethylhexyl) sebacate, di-(methy-lcyclohexyl) adipate and the like.

The process is preferably conducted with agitation of the reaction mixture. Although agitation is not critical to the success or failure of the process, its use is preferred since it accomplishes a smooth and even reaction rate.

The time required for the process varies depending on the other reaction variables. In general, however, a time period from about minutes to about 24 hours is sufficient.

In general, my process is carried out at temperatures between about to about 180 C. Preferably, however, temperatures in the range from about to about C. are employed since, within this range, relatively higher yields are obtained with a minimum of undesira'ble side reactions. The pressure under which the process is carried out is not critical. Pressure is, however, cnitical in the sense that the acetylene pressure within the reaction system must be sufficiently high to put acetylene in solution so that it can react with the manganese carbonyl compound. In general, acetylene pressures ranging from 100 to about 5,000 p.s.i.-g. are employed. A preferable range of acetylene pressures is from about 200 to about 1,000 p.s.i.g.

The reaction may be carried out under a blanketing atmosphere of an inert gas such as nitrogen, helium argon and the like. Normally, the acetylene reactant, which is present in the system as a gas, blankets the reaction mixture so as to prevent contacting of the reactants or products by an oxidizing gas such as oxygen. In some cases, it is desirable to use an inert gas in the system in conjunction with the acetylene reactant. In such cases, function of the inert gas is primarily to control the pressure within the system without increasing the acetylene concentration.

The product, dihydropentalenyl manganese tricar-bonyl, has very desirable physical properties for use as an antiknock. It is relatively stable, both thermally and oxidatively, and it is a liquid having a boiling point of 144 C. at 18 mm. Hg. It is, therefore, readily transportable in large quantities since it can be handled in pipe lines by means of conventional pumping equipment.

3 Further, it is easily blended with hydrocarbon fuels due to the fact that it is a liquid.

The product, dihydropentalenyl manganese tricarbonyl, can be separated from the reaction mixture by conventional means such as distillation or chromatography.

To further illustrate my novel process, there are presented the following examples in which'all parts and percentages are by weight unless otherwise indicated.

EXAMPLE I EXAMPLE II A mixture comprising 20 parts of bromomanganese pentacarbonyl, 45 parts of acetylene and 630 parts of tetrahydrofuran. was charged to an autoclave at 150 C. for four hours. Prior to heating, the autoclave had been pressurized with nitrogen to a total pressure of 1,050 p.s.i.g. After heating, the reaction mixture was allowed to remain in (the autoclave overnight, and the final pressure was 925 p.s.i.g. at 21 C. On discharge of the reaction mixture under nitrogen, it was observed as a clear light-orange solution containing a small amount of dispersed solids. The reaction mixture was filtered under nitrogen, excess ltetrahydrofunan was removed from the filtrate by heating under vacuum, and there was obtained a brown solid and a small amount of a viscous liquid. The brown solid and viscous liquid were dissolved in petroleum ether, and the petroleum ether was removed under vacuum to give a light-orange viscous liquid. The liquid product was submitted for analysis, and there was found: Mn, 22.5; C, 54.9 and H, 3.19 percent. Calculated for C H Mn(CO) Mn, 22.7; C, 54.6 and H, 2.91 percent. The analysis of the product and its infrared spectrum clearly identified it as dihydropentalenyl manganese tricarbonyl.

. EXAMPLE III Twenty parts of benzoylmanganese pentacarbonyl was dissolved in 710 parts of anhydrous tetrahydrofuran and charged to a stainless steel autoclave to which was added approximately 70 pants of acetylene. The autoclave was heated at 130 C. for 4.5 hours, allowed to cool overnight, and the reaction mixture was discharged under nitrogen. Filtration removed 1.5 parts ofan intractable non-volatile brown solid and evaporation of the solvent from the filtrate at reduced pressure and room temperature left an oily brown residue. Evaporative distillation of the oily brown residue at 0.05 mm. Hg and 90 C. yielded an orange liquid condensate which was contaminated with a yellow solid. The condensate was dissolved in low-boiling petroleum ether, was chromatographed on alumina and was eluted with petroleum ether. Removal of solvent from the initial chromatographic fraction followed by e-vaporati've distillation at 0.05 mm. Hg and 50 C. yielded 0.6 part of a yellow-orange liquid which was contaminated with the previously mentioned yellow solid. This solid was removed from the liquid mechanically to leave only the yellow-orange liquid.

The major chromatographic fraction, when evaporatively distilled at 0.05 mm. Hg and 50 C. (after removal of the petroleum ether, gave 3.25 parts of a yelloworange liquid. On analysis of the liquid, which was identical to the yellow-orange liquid obtained from the 4 initial chromatographic fraction, there was found: Mn, 22.6; C, 55.2 and H, 3.45 percent. Calculated for C H Mn(CO') Mn, 22.7; C, 54.6 and H, 22.91 percent. On the basis of the elemental analysis and also the infrared absorbencies of the liquid product, it was clearly identified as dihydropentalenyl manganese tricarbonyl.

EXAMPLE IV A solution comprising parts of methylmianganese pentacarbonyl and 620 parts of tetrahydrofuran was placed in an autoclave and saturated with acetylene at 17 C. and 70 p.s.i.g. The resulting solution was heated to 150 C. and kept at this temperature for seven hours.

After cooling the reaction vessel and venting it, the solvent was removed in vacuo, and the remaining oil was distilled. There was obtained 65 parts of a yellow oil which was shown by its infrared spectrum to be dihydropentalenyl manganese tricarbonyl. On hydrogenation of this compound in the presence of Raney nickel, it was reduced to form tetrahydropentalenyl manganese tricarbonyl.

EXAMPLE V A solution comprising one mole of phenylmanganese pentacarbonyl in diethylene glycol dimethyl ether is charged to an evacuated autoclave along with 50 moles of acetylene. The autoclave is heated to a temperature of 115 C. at a pressure of 4,000 p.s.i.g. and maintained at this temperature for 24 hours. The autoclave is then cooled, and the reaction product is discharged under ni trogen. The reaction product is filtered; the solvent is removed from the filtrate by heating it at reduced pressures, and the residue is distilled to give a good yield of dihydropentalenyl manganese tricarbonyl.

EXAMPLE VI A solution comprising one mole of palmitoylmanganese pen-tacarbonyl in toluene is charged to an evacuated reaction vessel. There are then added eight moles of acetylene, and the reaction vessel is heated with stirring to a temperature of 180 C. and a pressure of 100 p.s.i.g. After maintaining the reaction vessel at this temperature for six hours, it is cooled, and the contents are discharged under nitrogen. The reaction product is filtered; solvent is removed from the'filtrate, and the residue is distilled to give a good yield of dihydropen talenyl manganese tricarbonyl.

EXAMPLE VII Twenty moles of acetylene are charged to a reaction vessel along with a solution comprising one mole of acrylylmanganese pentacarbonyl in tetrahydrofuran. The

reaction vessel is heated to a temperature of 140 C. at a pressure of 200 p.s.i.g. and maintained at this temperature for four hours with stirring. The reaction vessel is cooled; the contents are discharged under nitrogen, and

. a good yield of dihydropentalenyl manganese tricarbonyl is obtained by means of distillation as in the previous examples.

EXAMPLE VIII anese tricarbonyl.

EXAMPLE IX A solution of 1.5 moles of perlluoroacetylmanganese of the remainingresidue gives a good yield of dihydropentalenyl mang pentacarbonyl in acetone is charged to an evacuated autoclave. Eighteen moles of acetylene are then charged to the autoclave, and its is heated to 150 C. at a pressure of 500 p.s.i.g. After heating for hours, the autoclave is cooled, and the contents are discharged under nitrogen. A good yield of dihydropentalcnyl manganese tricarbonyl is obtained from the reaction product by means of distillation as in the previous examples.

EXAMPLE X One mole of n-butylmanganese pentaoarbonyl dissolved in di-n-butyl ether is charged to a reaction vessel along with 25 moles of acetylene. The vessel is then heated to 170 C. at a pressure of 400 p.s.i.g. and maintained at this temperature for three hours. The vessel is cooled, and the contents are discharged under nitrogen. Filtration of the reaction product followed by removal of solvent from the filtrate and distillation of the resulting residue gives a good yield of dihydropentalenyl manganese tricarbonyl.

EXAMPLE XI One mole of p-tolylmanganese pentacarbonyl dissolved in benzene is charged to a reaction vessel along with 30 moles of acetylene. The reaction vessel is heated to 130 C. at a pressure of 800 p.s.i.g. and maintained at this temperature for five hours. The vessel is then cooled, and the contents are discharged under nitrogen. A good yield of dihydropentalenyl manganese tricarbonyl is obtained from the reaction product by means of distillation as in the previous examples.

EXAMPLE XII A 0.242 part sample of dihydropentalenyl manganese tricarbonyl was dissolved in 19.6 parts of ethanol and charged to a reaction vessel. A small quantity of Raney nickel was added, and hydrogen was introduced into the system at one atmosphere of pressure. Hydrogenation occurred as soon as the reaction mixture was stirred. The amount of hydrogen which was absorbed closely approximated the theoretical amount of hydrogen necessary to hydrogenate the double bond in dihydropentalenyl manganese tricarbonyl. The product was discharged; the solvent was removed in vacuo, and the residual oil was cooled. The residual oil solidified and was sublimed to give yellow crystals having a rhombic crystalline form and a melting point of 34.5-35.5 C. On analysis, there was found: C, 54.3; H, 3.9; Mn, 22.4 percent. Calculated for C H MnO C, 54.2; H, 3.7; M-n, 22.5 percent. On the basis of the elemental analysis and the quantity of hydrogen absorbed in the reaction, the compound was identified as tetrahydropentalenyl manganese tricarbonyl.

In order to definitely prove the structure of the dihydropentalenyl manganese tricarbonyl compound, an independent synthesis was made of the tetrahydropentalenyl manganese tricarbonyl which was obtained on hydrogenation of the dihydropentalenyl manganese tricarbonyl. This independent synthesis is presented in the following example.

EXAMPLE 2611 A solution comprising 21.4 grams of lithium aluminum tri(tert-butoxy) hydride in 49 ml. of diethylene glycol dimethyl ether was added to a stirred solution comprising 16.5 grams of [(chloroformly) cyclopentadienyl] manganese tricarbonyl in 215 ml. of diethylene glycol dimethyl ether. The addition took place over a one and onehalf hour period during which the temperature of the [(chloroformyl)cyclopentadienyl] manganese tricarbonyl solution was maintained at 78 C. After addition was complete, the reaction mass was allowed to warm to room temperature. It was poured onto ice and acidified to Congo red with hydrochloric acid. The mixture was extracted with ether; the ether was dried, and the solvent was removed to yield an oil. The oil was distilled to give 11.6 grams (81 percent yield) of formyl)cyclopentadienyl] manganese tricarbonyl which was a low-melting solid.

A mixture comprising 11.6 grams of [(formyl)cyolopentadienyl] manganese tricarbonyl, 5.3 grams of malonic acid and 4.66 grams of a-picoline was heated on a steam bath for two hours. Evolution of 800 ml. of gas was observed. The theoretical evolution of gas was 1100 ml. The reaction mixture was poured into water, and this was extracted with ether. The ether extracts were further extracted with carbonate solution. Acidification of the carbonate extracts gave 8.3 grams (61 percent yield of [(Z-carboxyvinyl)cyclopentadienyl] manganese tricarbonyl which was a yellow solid. The melting point of the product, after recrystallization from chloroform-benzene solution, was 156-157 C.

A solution comprising 0.5 gram 10f [(2-oarboxyvinyl)- cyolopentadienyl] manganese tricarbonyl in 20 of ethanol was hydrogenated over Raney nickel at atmospheric pressure. After one hour, the hydrogen uptake had ceased, and the reaction mixture was then filtered and the solvent removed. Recrystallization of the remaining oil from chloroform-petroleum ether solution gave 0.3 gram (60 percent yield) of [(Z-carboxyethyl)cyclopentadienyl] manganese tricarbonyl which was a yellow solid having a melting point of l36138 C.

To 40 grams of polyphosphoric acid was added 4.67 grams of [(2-carboxyethyl)cyclopentadienyl] manganese tricarbonyl. The mixture was stirred and heated at 70'- C. for three hours. After pouring onto ice, the mixture was extracted with ether. The ether extracts were further extracted with carbonate solution after which they were dried and the solvent was removed to yield 2.8 grams (65 percent yield) of tetrahydro-4-oxopentalenyl manganese tricarbonyl.

To a mixture comprising five grams of amalgamated zinc, 30 of water, 30 ml. of hydrochloric acid, 10 ml. of toluene and three ml. of dioxane was added one gram of tetrahydro-4-oxopentalenyl manganese tricarbonyl. The mixture was stirred at reflux for 24 hours. At the three hour mark, 30 ml. of hydrochloric acid and five grams of amalgamated zinc were added, and at the 18 hour mark 10 ml. of hydrochloric acid were added. After the reaction mixture had cooled, the liquid was decanted and extracted with ether. The ether extracts were extracted several times with a 10 percent solution of hydrochloric acid after which they were dried, and the solvent was removed. The residual oil was chromatographed on alumina with benzene. The first fraction was taken and distilled, after the removal of the solvent, to yield 0.3 gram (32 percent yield) of a yellow solid hav ing a melting point of 34.5-35.5 C. This was shown by means of infrared absorption, mixed melting point, vaporphase chromatography and X-ray diifraction patterns to be tetrahydropentalenyl manganese tricarbonyl which was in all respects identical to the tetrahydropentalenyl manganese tricarbonyl produced by hydrogenation of dihydro pentalenyl manganese tricarbonyl as in Example XII.

A further embodiment of my invention involves the use of dihydropentalenyl manganese tricarbonyl as an antiknock agent in liquid hydrocarbon fuel used in sparkignition internal combustion engines. For this use, I provide liquid hydrocarbon fuel of the gasoline boiling range containing from about 0.05 to about 10 grams per gallon of manganese as the compound dihydnopentalenyl manganese tricarbonyl. It is found that these compositions, when employed as fuels for a spark-ignition internal combustion engine, greatly reduce the tendency of the engine to knock.

Preferred compositions of my invention comprise a hydrocarbon of the gasoline boiling range containing from about 1.0 to about 6.0 grams of manganese per gallon of fuel as the compound dihydropentalenyl manganese tricarbonyl. This range of metal concentration is preferred since it is found that superior fuels result from its employment.

The base fuels used to prepare the compositions of my invention have a wide variation of compositions. They generally are petroleum hydrocarbons and are usually blends of two or more components containing a mixture of many individual hydrocarbon compounds. These fuels can contain all types of hydrocarbons, including parafiins, both straight and branched chain; olefins; cycloaliphatics containing paraflin or olefin side chains; and aromatics containing aliphatic side chains. The fuel type depends on the base stock fuom which it is obtained and on the method of refining. For example, it can be a straight run or processed hydrocarbon, including thermally cracked, catalytically cracked, reformed fractions, etc. When used for spark-fired engines, the boiling range of the compo nents in gasoline can vary from zero to about 430 F., although the boiling range of the fuel blend is often found to be between an initial boiling point of from about 80 F. to 100 F. and a final boiling point of about 430 F. While the above is true for ordinary gasoline, the boiling range is somewhat more restricted in the case of aviation gasoline. Specifications for, the latter often call for a boiling range of from about 82 F. to about 338 F., with certain fractions of the fuel boiling away at particular intermediate temperatures.

These fuels often contain minor quantities of various impurities. One such impurity is sulfur, which can be present either in a combined form as an organic or inorganic compound, or as elemental sulfur. The amounts of such sulfur can vary in various fuels about 0.003 percent to about 0.30 percentby weight. Fuels containing quantities of sulfur, both lesser and greater than the range of amounts referred to above, are also known. These fuels also often contain added chemicals in the nature of antioxidants, rust inhibitors, dyes, and the like.

' The compound of my invention can be added directly to the hydrocarbon fuel, and the mixture then subjected to stirring, mixing or other means of agitation until a homogeneous fluid results. In addition to my compound, the fuel may have added thereto antioxidants, metal deactivators, halohydrocarbon scavengers, phosphorus compounds, anti-rust and anti-icing agents, and supplementary wear inhibitors. The following examples are illustrative of improved fuels of my invention containing a dihydropentalenyl manganese tricarbonyl, and also a method for preparing said improved fuels.

EXAMPLE XIV To 1000 gallons of commercial gasoline having a gravity of 59. API, an initial boiling point of. 98 F. and a. final boiling point of 390 F. which contains 45.2 volume percent parafiins, 28.4 volume percent olefins and 25.4

volume percent aromatics is added 10.0 grams per gallon of manganese as dihydropentalenyl manganese tricarbonyl to give a fuel of enhanced octane quality.

EXAMPLE XVI Dihydropentalenyl manganese tricarbonyl is added'in amount 'sufiicient to give a manganese concentration of 6.0 gram' per gallon to a gasoline having an initial boiling point of 93 F., a final boiling point of 378 'F. and an API gravity of 562.

EXAMPLE XVII To a liquid hydrocarbon fuel containing 49.9 volumepercent parafiins, 15.9 volume percent olefins and 34.2 volume percent aromatics and which has an API gravity of 51.5, an intial boiling point of 11 F. and a final boiling point of 394 F. is added dihydropentalenyl manganese tricarbonyl to give a manganese concentration of 1.0 gram per gallon.

EXAMPLE XVIII To the fuel of Example XVII is added dihydropental enyl manganese tricarbonyl in amount such that the manganese concentration is 3.0 grams per gallon.

A further embodiment of the present invention com-- prises a liquid hydrocarbon fuel of the gasoline boiling range containing an organolead antiknock agent and in addition dihydropentalenyl manganese tricarbonyl as defined previously. In this embodiment of the invention, it is often desirable that the fuel contain also conventional halohyclrocarbon scavengers or corrective agents as conventionally used with organolead antiknock agents. When an organolead antiknock agent is employed, it may be present in the fuel in concentrations up to about eight grams of lead per gallon. In the case of aviation fuels, up to 6.34 grams of lead may be employed.

For each gram of lead, there may be present from about 0.008 to about 10 grams of manganese as dihydropentalenyl manganese tricarbonyl. A preferred range comprises those compositions containing from about 0.01 to about six grams of manganese as dihydropentalenyl manganese tricarbonyl for each gram of lead as an organolead compound.

A preferred embodiment of my invention comprises a liquid hydrocarbon fuel of the gasoline boiling range containing from about 0.5 to about 6.34 grams of lead per gallon as an organolead antiknock agent and from about 0.008 to about one gram of manganese per gallon as dihydropentalenyl manganese tricarbonyl. A further preferred aspect of my invention comprises compositions, as defined previously, in which the manganese concentration ranges from about 0.01 to about 0.5 and most preferably, from about 0.01 to about 0.3 gram of manganese per gallon. These ranges of metal concentrations are preferred as it has been found that especially superior fuelsparticularly from a cost-elfectiveness standpointresult from their use.

The organolead :antiknock agents are ordinarily hydrocarbolead compounds including tetraphenyllead, dimethyldiphenyllead, tetrapropyllead, dimethyldiethyllead, tetramethyllead and the like. Tetraethyllead is preferred as it is most commonly available as a commercial antiknock agent. It is also convenient in the case where organolead antiknock agents are employed to premix into a fluid the dihydropentalenyl manganese tricarbonyl, the organolead antiknock "agent and supplementary agents, such as scavengers, antioxidants, dyes and solvents, which fluids are later added to the liquid hydrocarbon fuel to be improved.

Where halohydrocarbon compounds are employed as scavenging agents, the amounts of halogen used are given in terms of theories of halogen. A theory of halogen is defined as the amountof halogen which is necessary to react completely with the metal present in the antiknock mixture to convert it to the metal dihalide, as for example, lead dihalide. In other words, a theory of halogen represents two atoms of halogen for every atom of lead present. In like manner, a theory of phosphorus is the amount of phosphorus required to convert the lead present to lead orthophosphate, Pb (PO.,) that is, a theory of phosphorus represents two atoms of phosphorus for every three atoms of lead. 'One theory of arsenic, antimony and bismuth is defined in the same general way. That is, one theory thereof is two atoms of the element per each three atoms of lead.

The halohydrocarbon scavengers which can be employed in the compositions of this invention can be either aliphatic or aromatic halohydrocarbons or a combination of the two having halogen attached to carbon in either the aliphatic or aromatic portion of the molecule. The scavengers may also be carbon, hydrogen and oxygen containing compounds, such as haloalkyl ethers, halohydrins, halo ethers, halonitro compounds, and the like. Still other examples of scavengers that may be used in the fuels of this invention are illustrated in U.S. Patents 1,592,954; 1,668,022; 2,398,281; 2,479,900; 2,479,901; 2,479,902; 2,479,903; 2,496,983; 2,661,379; 2,822,252; 2,849,302; 2,849,303; and 2,849,304. Mixtures of different scavengers may also be used and other scavengers and modifying agents, such as phosphorus compounds, may also be included. Concentrations of organic halide scavengers ranging from about 0.5 to about 2.5 theories based on the lead are usually sufiicient, although greater or lesser amounts may be used. See, for example, the desoription of scavenger concentrations and proportions given in U.S. Patent 2,398,381. Such concentrations and proportions can be successfully used in the practice of this invention.

When used in the compositions of this invention, phosphorus, arsenic, antimony and bismuth compounds have the property of altering engine deposit characteristics in several helpful ways. Thus, benefits are achieved by including in the compositions of this invention one or more gasoline-soluble organic compounds of the elements of group VA of the periodic table, which elements have atomic numbers 15 through 83. The periodic table to which reference is made is found in Langes Handbook of Chemistry, 7th Edition, pages 58-59. One effect of these group VA compounds is to alter the deposits so that in the case of spark plugs the resulting deposits are less conductive. Thus, imparted to the spark plug is greater resistance to fouling. In the case of combustion chamber surface deposits, the group VA element renders these deposits less catalytic with respect to hydrocarbon oxidation and thus reduces surface ignition. In addition, these group VA elements in some way inhibit deposit build up on combustion chamber surfaces, notably exhaust valves. This beneficial effect insures excellent engine durability. In particular, excellent exhaust valve life is assured. Of these group VA elements the use of gasoline-soluble phosphorus compounds is preferred from the cost-effectiveness standpoint. Applicable phosporus additives include the general organic phosphorus compounds, such as derivatives of phosphoric and phosphorus acids. Representative examples of these compounds include trimethylphosphate, trimethylphosphite, penyldimethylphosphate, triphenylphosphate, tricresylphosphate, tri-fi-chloropropyl thionophosphate, tributoxyethylphosphate, xylyl dimethylphosphate, and other alkyl, aryl, aralkyl, alkaryl and cycloalkyl analogues and homologues of these compounds. Phenyldimethylphosphates in which the phenyl group is substituted with up to three methyl radicals are particularly preferred because they exhibit essentially no antagonistic effects upon octane quality during engine combustion. Other suitable phosphorus compounds are exemplified by dixylyl phosphoramida-te, tributylphosphine, triphenylphosphine oxide, tricresyl thiophosphate, cresyldiphenylphosphate, and the like. Gasoline-soluble compounds of arsenic, antimony and bismuth corresponding to the above phosphorus compounds are likewise useful in this respect. Thus, use can be made of various alkyl, cycloalkyl, aralkyl, aralkyl, aryl and/ or alkaryl, arsenates, arsenites, antimonates, antimonites, bismu-thates, bismu-thites, etc. Tricresyl arsenite, tricumenyl arsenate, trioctyl antimonate, triethyl antimonite, diethylphenyl bismuthate and the like serve as examples. Other very useful arsenic, antimony and bismuth compounds include methyl arsine, trimethyl arsine, triethyl arsine, triphenyl arsine, arseno benzene, triisopropyl bismuthine, tripentyl stibine, tricresyl stibine, trixylyl bismuthine, tricyclohexyl bismuthine and phenyl dicresyl bismuthine. From the gasoline solubility and engine inductibility standpoints, organic compounds of these group VA elements having up to about 30 carbon atoms in the molecule are preferable. Concentrations of these group VA compounds ranging from about 0.05 to about 10 one theory based on the lead normally sufiice. In other words, the foregoing technical benefits are achieved when the atom ratio of group VA element-to-lead ranges from about 0.1 :3 to about 2:3.

A further embodiment of my invention comprises antiknock fluids containing an organolead antiknock agent, dihydropentalenyl manganese tricarbonyl, and, optionally, a scavenger for the organolead compound. The quantities of manganese and scavenger present with respect to the quantity of lead present are the same as set forth in the preceding paragraphs in describing a hydrocarbon fuel containing these various components. Thus, the fluid can be blended with a hydrocarbon base fuel to give the fuel compositions described above.

The following examples are illustrative of fuels and fluids containing organolead compounds in combination with dihydropentalenyl manganese tricarbonyl.

EXAMPLE XIX To 1000 gallons of a gasoline containing 46.2 percent paraffins, 28.4 percent olefins, and 25.4 percent aromatic which has a final boiling point of 390 F. and an API gravity of 590 and which contains three milliliters of tetraethyllead as 62-mix (one theory of ethylene dichloride and 0.5 theory of ethylene dibromide) is added sufficient dihydropentalenyl manganese tricarbonyl to give a manga nese concentration of six grams per gallon.

EXAMPLE XX A fluid for addition to gasoline is prepared by admixing tetraethyllead, dihydropentalenyl manganese tricarbonyl and trimethylphosphate in amount such that for each gram of lead there is 0.01 gram of manganese and 0.1 theory of trimethylphosphate.

To demonstrate the effectiveness of hydrocarbon fuels blended with dihydropentalenyl manganese tricarbonyl according to the invention, tests were made on fuels to which no antiknock agent was added and fuels which were blended in accordance with this invention. These tests were conducted according to the Research Method. The Research Method of determining octane number of a fuel is generally accepted as a method of test which gives a good indication of fuel behavior in full scale automotive engines under normal driving conditions and is the method most used by commercial installations in determining the value of a gasoline additive. The Research Method of testing antiknocks is conducted in a single cylinder engine especially designed for this purpose and referred to as the CPR engine. This engine has a variable compression ratio and during the test the temperature of the jacket water is maintained at 212 -F. and the inlet air temperature is controlled at F. The engine is operated at a speed of 600 r.p.-m. with a spark advance of 13 before top dead center. The test method employed is more fully described in Test Procedure D90855 contained in the 1956 edition of ASTM Manual of Engine Test Methods for Rating Fuels. When tested in this manner, it is found that the addition of one gram of manganese per gallon as dihydropentalenyl manganese tricarbonyl causes a substantial increase in the octane number of a non-additive containing gasoline.

Further tests which were performed using the Research Method involved the base reference fuels which contained both a lead antiknock and halohydrocarbon scavengers. To the reference fuels was added dihydropentalenyl manganese tricarbonyl. In each case, a substantial gain in the octane number of the base fuel was noted.

These results are set forth in the following table. The reference fuel to which dihydropentalenyl manganese tricarbonyl was added comprised 40 percent by volume of toluene, 30 percent by volume of n-heptane, 20 percent by volume of diisobutylene, and 10 percent by volume of isooctane and contained three ml. of tetraethyllead per gallon as 62-mix. 62-mix is a commercial antiknock fluid comprising tetraethyllead, 1.0 theory of ethylene dichloride and 0.5 theory of ethylene dibromide.

11 Table I.-Research Octane Number Concentration of dihydropentalenyl mangagese tricarbonyl expressed as grams or manganese per gallon} Similar results are obtained using concentrations of the dihydropentalenyl manganese tricarbonyl up to 10 grams of manganese for each gram of lead in the fuel.

As shown by the above data, dihydropentalenyl manganese tricarbonyl is extremely efiective as a supplemental antiknock. As is the case with most supplemental antiknocks, it is generally more effective as a supplement at low concentrations, and its effectiveness is diminished as its concentration is increased.

A further use for my compound is in gas phase metal plating. In this application, the compound is thermally decomposed in an atmosphere of a reducing gas such as hydrogen or a neutral atmosphere such as nitrogen to form metallic films on a sub-strate material. These films have a Wide variety of applications. They may be used in forming conductive surfaces such as employed in a printed circuit, in producing a decorative effect on a sub-strate material, or in applying a corrosion-resistent coating to a sub-strate material.

My compound also finds application as an additive to lubricating oils and greases to impart improved lubricity characteristics thereto. Further, my compound may be incorporated in paints, varnish, printing inks, synthetic resins of the drying oil type, oil enamels and the like to impart improved drying characteristics to such compositions. Another important utility of my compound is its use as a chemical intermediate in the preparation of metal-containing polymeric materials.

My compound, dihydropentalenyl manganese tricarbonyl, may also be used as an additive to distillate fuels generally such as those used in home heating, jet fuels, and diesel fuels. In this application, my compound serves to reduce smoke and/ or soot formation on combustion of the fuel.

Having fully defined the novel compounds of my invention, their novel mode of preparation and their manifold utilities, I desire to be limited only within the lawful scope of the appended claims.

I claim:

1. Process comprising reacting acetylene with a manganese carbonyl compound having the formula, ZMn(CO) in which Z is a monovalent substituent group selected from the class consisting of halides and organic radicals having up to 16 carbon atoms, selected from the class consisting of alkyl, aralkyl, aryl, alkaryl, acyl, cycloalkyl, alkenyl and alkynyl radicals.

2. The process of claim 1 wherein the reaction is carried out in the presence of a non-reactive organic solvent.

3. The process of claim 2 wherein from about eight to about moles of acetylene are employed for each mole of said manganese carbonyl compound.

4. The process of claim 3 wherein the temperature at which the reaction is conducted ranges from between about to about 180 C.

5. The process of claim 3 wherein the temperature at which the reaction is carried out ranges between about to about C.

6. The process of claim 4 wherein the acetylene pressure in the reaction system ranges from between about 100 to about 5,000 p.s.i.g.

7. The process of claim 5 wherein the acetylene pressure in the system ranges from about 200 to about 1,000 p.s.i.g.

8. The process of claim 7 wherein the reaction is carried out in the presence of a non-reactive polar organic solvent.

9. Dihydropentalenyl manganese tricarbonyl.

10. Process comprising reacting dihydropentalenyl manganese tricarbonyl with hydrogen to form tetrahydropentalenyl manganese tricarbonyl.

References Cited in the file of this patent UNITED STATES PATENTS 2,818,417 Brown et al. Dec. 31, 1957 2,881,062 Bishop Apr. 7, 1959 2,898,354 Shapiro et a1. Aug. 4, 1959' 2,933,380 Kegelman Apr. 19, 1960 FOREIGN PATENTS 229,362 Australia July 17, 1958 OTHER REFERENCES Chem. and Eng. News, 36, pages 43-44, May 5, 1958.

Schrauzer: Chem. and Industry, pages 1403-1404, October 25, 1958.

Hubel et al.: J. Inorg. Nuc. Chem., 9, pages 204-210, March 1959. 

1. PROCESS COMPRISING REACTING ACETYLENE WITH A MANGANESE CARBONYL COMPOUND HAVING THE FORMULA, ZMN(CO)5, IN WHICH Z IS A MONOVALENT SUBSTITUENT GROUP SELECTED FROM THE CLASS CONSISTING OF HALIDES AND ORGANIC RADICALS HAVING UP TO 16 CARBON ATOMS, SELECTED FROM THE CLASS CONSISTING OF ALKYL, ARALKYL, ARYL, ALKARYL, ACYL, CYCLOALKYL, ALKENYL AND ALKYNYL RADICALS. 